US11352457B2 - Fluorine-containing compound having unsaturated bond, and surface modifier using the same - Google Patents

Fluorine-containing compound having unsaturated bond, and surface modifier using the same Download PDF

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US11352457B2
US11352457B2 US16/025,014 US201816025014A US11352457B2 US 11352457 B2 US11352457 B2 US 11352457B2 US 201816025014 A US201816025014 A US 201816025014A US 11352457 B2 US11352457 B2 US 11352457B2
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fluorine
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carbon atoms
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Shinichiro Nakamura
Norihisa Kondo
Takayuki Yamasaki
Tomohiro SHIRAI
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Tosoh Finechem Corp
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Definitions

  • the present invention relates to a novel fluorine-containing compound having an unsaturated bond, which is useful as a raw material of a surface modifier or the like.
  • Fluorine has unique properties such as a high electronegativity and a low polarizability, and is used as an element useful for functional materials utilizing properties such as heat resistance, chemical resistance, water repellency/oil repellency, a low friction property and a low refraction property.
  • a compound having a perfluoroalkyl group having 8 or more carbon atoms has been heretofore used for functional products imparting water repellency and/or oil repellency, but such a compound has been problematic in terms of accumulation in the environment and the human body, and hazardousness.
  • a method which includes forming a compound having a perfluoroalkyl group whose fluorine is partially replaced with hydrogen, and thus using the compound as a structure of a perfluoroalkyl group unit having 6 or less carbon atoms, which is deemed to be low in accumulation in the living body, for a modifier (see, for example, Patent Document 2 and Patent Document 3).
  • Patent Document 1 International Publication No. WO 2009/087981
  • Patent Document 2 Japanese Patent No. 5146455
  • Patent Document 3 Japanese Patent Laid-Open No. 2014-040373
  • the present invention provides a novel fluorine-containing compound serving as a new material exerting excellent, high water-repellent and oil-repellent effects and having an enhanced surface modification performance as compared with a conventional one, as well as a surface modifier using the compound.
  • the present inventors have found that a compound containing a fluorine-containing long-chain group having an unsaturated bond, shown below, is used for surface modification to result in a high water-repellent and oil-repellent performance, thereby leading to completion of the present invention.
  • the present invention is an invention according to a fluorine-containing compound represented by the following general formula (1) or the following general formula (2), or the following general formula (5):
  • Rf 1 (CR 1 ⁇ CR 2 —X—Rf 2 ) n —Y—Z (1)
  • Rf 1 represents a perfluoroalkyl group having 1 to 6 carbon atoms, with a CF 3 terminal,
  • Rf 2 represents a perfluoroalkylene group having 1 to 6 carbon atoms
  • R 1 and R 2 each independently represent a hydrogen atom or a fluorine atom
  • n an integer of 1 to 5
  • X is absent in the formula (1) or in the formula (2), or represents CH 2 , O or S,
  • Y represents a linking group
  • Z represents any structure of the following (i) to (iii):
  • M 1 and M 2 each independently represent a hydrogen atom, an ammonium salt, an organic amine salt, or an alkyl group having 1 to 4 carbon atoms;
  • L represents a hydrolyzable group or a hydroxyl group
  • L′ represents a hydrocarbon group having 1 to 6 carbon atoms
  • k represents an integer of 1 to 3
  • the L and L′ groups may be different from or the same as each other.
  • the present invention relates to the fluorine-containing compound wherein Rf 2 represents a linear perfluoroalkylene group having 1 to 6 carbon atoms: Rf 3 —(CF ⁇ CR 3 —CR 4 ⁇ CF—Rf 4 ) n —Y—Z (5)
  • Rf 3 represents a perfluoroalkyl group having 1 to 5 carbon atoms, with a CF 3 terminal,
  • Rf 4 represents a perfluoroalkylene group having 1 to 5 carbon atoms
  • R 3 and R 4 each independently represent a hydrogen atom or a fluorine atom
  • n an integer of 1 to 5
  • Y represents a linking group
  • Z represents any structure of the following (i) to (iii):
  • M 3 and M 4 each independently represent a hydrogen atom, an ammonium salt, an organic amine salt, or an alkyl group having 1 to 4 carbon atoms;
  • L represents a hydrolyzable group or a hydroxyl group
  • L′ represents a hydrocarbon group having 1 to 6 carbon atoms
  • k represents an integer of 1 to 3
  • the L and L′ groups may be different from or the same as each other.
  • the present invention relates to the fluorine-containing compound described above wherein Rf 4 represents a linear perfluoroalkylene group having 1 to 5 carbon atoms.
  • the present invention relates to the fluorine-containing compound wherein Y is represented by the following general formula (8): (CH 2 ) l —Q—(CH 2 ) m (8)
  • a —CH ⁇ CH— structure is optionally included instead of —CH 2 CH 2 —;
  • Q is absent in the formula (8), or represents —OCONH—, —CONH—, —O—, —NH—, —CO—O—, —O—CO—, —NHCONH— or —C 6 H 4 —.
  • the present invention relates to the fluorine-containing compound wherein R 1 and/or R 2 represent(s) a hydrogen atom, and R 3 and/or R 4 represent(s) a hydrogen atom.
  • the present invention relates to the fluorine-containing compound wherein X is absent in the formula (1) or in the formula (2), or represents CH 2 .
  • the present invention relates to the fluorine-containing compound wherein the hydrolyzable group L represents Cl or OR 5 wherein R 5 represents an alkyl group having 1 to 4 carbon atoms.
  • the present invention relates to a surface modifier comprising the novel fluorine compound described above.
  • the fluorine-containing compound of the present invention is represented by the following general formula (1) or the following general formula (2).
  • Rf 1 (CR 1 ⁇ CR 2 —X—Rf 2 ) n —Y—Z (1)
  • Rf 1 (X—CR 1 ⁇ CR 2 —Rf 2 ) n —Y—Z (2)
  • an Rf 1 group is a perfluoroalkyl group having 1 to 6 carbon atoms, with a CF 3 terminal. While the structure may have a branched structure, it is considered that a linear perfluoroalkyl group easily has a self-assembled structure to easily form a monolayer on a glass surface, and therefore a linear perfluoroalkyl group is preferable.
  • an Rf 2 group is a perfluoroalkylene group having 1 to 6 carbon atoms. While the structure may have a branched structure, a linear perfluoroalkylene group is preferable.
  • Specific structures of the portion Rf 1 —(CR 1 ⁇ CR 2 —X—Rf 2 ) n — in the general formula (1) and the general formula (2) include C 2 F 5 —CH ⁇ CH—C 4 F 8 —, C 2 F 5 —CH ⁇ CF—C 4 F 8 —, C 2 F 5 —CF ⁇ CH—C 4 F 8 —, C 2 F 5 —CF ⁇ CF—C 4 F 8 —, C 2 F 5 —(CH ⁇ CH—C 4 F 8 ) 2 —, C 2 F 5 —(CH ⁇ CH—C 4 F 8 ) 3 —, C 2 F 5 —CH ⁇ CH—C 6 F 12 —, C 4 F 9 —CH ⁇ CH—C 4 F 8 —, C 4 F 9 —CH ⁇ CH—C 6 F 12 , C 6 F 13 —CH ⁇ CH—C 4 F 8 —, C 6 F 13 —CH ⁇ CH—C 6 F 12 —, C 2 F 5 —CH ⁇ CH—C 4 F 8 —, CF
  • Such structures can be each obtained by performing radical addition of an iodinated compound in the form of a combination of Rf 1 —I and CHR 1 ⁇ CR 2 —Rf 2 —I, or Rf 1 —CR 1 ⁇ CHR 2 and I—Rf 2 —I, or the like, and thereafter subjecting a structural portion of —CF 2 —CIR 1 —CHR 2 CF 2 — generated, to an HI-elimination or IF-elimination reaction.
  • a terminal iodine located opposite to the Rf 1 end can be treated with a proper reagent to thereby introduce a group such as olefin, alcohol or amine.
  • the “terminal iodine located opposite to the Rf 1 end” here means, for example, I (iodine) adjacent to C 4 F 8 in the case of C 6 F 13 —CH ⁇ CH—C 4 F 8 —I, and means an unreacted terminal iodine remaining after the addition reaction, located at the Rf 2 side.
  • Rf 1 —CR 1 ⁇ CR 2 —Rf 2 —I can be subjected to addition with ethylene, Rf 1 —CR 1 ⁇ CR 2 —Rf 2 —CH 2 CH 2 I consequently obtained can be hydrolyzed to synthesize Rf 1 —CR 1 ⁇ CR 2 —Rf 2 —CH 2 CH 2 OH, and thereafter Rf 1 —CR 1 ⁇ CR 2 —Rf 2 —CH 2 CH 2 OH can be bound to a proper introduction material of a Z group, such as chlorophosphoric acid ester, acryloyl chloride or isocyanate group-containing trialkoxysilane according to a known method to thereby provide a fluorine-containing compound of interest.
  • a Z group such as chlorophosphoric acid ester, acryloyl chloride or isocyanate group-containing trialkoxysilane according to a known method to thereby provide a fluorine-containing compound of interest.
  • R 1 and R 2 each independently represent a hydrogen atom or a fluorine atom and n represents an integer of 1 to 5. Further preferably, R 1 and/or R 2 represent(s) a hydrogen atom.
  • X is absent in the general formula (1) or the general formula (2), or represents CH 2 , O or S. That is, X can impart high improvement performance, even when X is absent or represents CH 2 , O or S, as long as an olefin compound represented by the general formula (1) or the general formula (2) is obtained.
  • the general formula (1) and the general formula (2) each represent Rf 1 —(CR 1 ⁇ CR 2 —Rf 2 ) n —Y—Z.
  • the formula (1) represents Rf 1 —(CR 1 ⁇ CR 2 —CH 2 —Rf 2 ) n —Y—Z and the formula (2) represents Rf 1 —(CH 2 —CR 1 ⁇ CR 2 —Rf 2 ) n —Y—Z.
  • Rf 1 —I and CHR 1 ⁇ CR 2 —Rf 2 —I or Rf 1 —CR 1 ⁇ CHR 2 and I—Rf 2 —I can be subjected to radical addition and thereafter HI-elimination to thereby synthesize Rf 1 —CR 1 ⁇ CR 2 —Rf 2 —I.
  • Rf 1 —CFR 1 —CR 2 ⁇ CH 2 and I—Rf 2 —I or Rf 1 —I and CH 2 ⁇ CHR 1 —CFR 2 —Rf 2 —I can be subjected to radical addition and thereafter an IF-elimination reaction to thereby synthesize Rf 1 —CR 1 ⁇ CR 2 —CH 2 —Rf 2 —I or Rf 1 —CH 2 —CR 1 ⁇ CR 2 —Rf 2 —I, respectively.
  • a compound where X ⁇ O or S can be obtained by dehydrohalogenation of a compound represented by Rf 1 —X—CR 1 R 3 —CR 2 R 4 —Rf 2 —I or Rf 1 —CR 1 R 3 —CR 2 R 4 —X—Rf 2 —I (one of R 3 and R 4 represents H and the other thereof represents an element selected from Cl, Br and I).
  • Z in the general formula (1) and the general formula (2) represents a surface modification group represented by the following general formula (3) or the following general formula (4).
  • M 1 and M 2 each independently represent a hydrogen atom, an ammonium salt, an organic amine salt, or an alkyl group having 1 to 4 carbon atoms.
  • fluorine-containing compound of the present invention is represented by the following general formula (5): Rf 3 —(CF ⁇ CR 3 —CR 4 ⁇ CF—Rf 4 ) n —Y—Z (5)
  • an Rf 3 group is a perfluoroalkyl group having 1 to 5 carbon atoms, with a CF 3 terminal. While the structure may have a branched structure, it is considered that a linear perfluoroalkyl group easily has a self-assembled structure to easily form a monolayer on a glass surface, and therefore a linear perfluoroalkyl group is preferable.
  • an Rf 4 group is a perfluoroalkylene group having 1 to 5 carbon atoms. While the structure may have a branched structure, a linear perfluoroalkylene group is preferable.
  • Such structures can be each obtained by performing radical addition of an iodine compound in the form of a combination of Rf 3 —CF 2 —I and CHR 3 ⁇ CR 4 —CF 2 —Rf 4 —I, or Rf 3 CF 2 —CR 3 ⁇ CHR 4 and I—CF 2 —Rf 4 —I, or the like and thereafter subjecting a structural portion of —CF 2 —CIR 3 —CHR 4 CF 2 — generated, to an HI-elimination or IF-elimination reaction.
  • a terminal iodine located opposite to the Rf 3 end can be treated with a proper reaction test material to thereby introduce a group such as olefin, alcohol or amine.
  • the “terminal iodine located opposite to the Rf 3 end” here means, for example, I (iodine) adjacent to C 5 F 10 in the case of C 5 F 11 —CF ⁇ CH—CH ⁇ CF—C 5 F 10 —I, and means an unreacted terminal iodine remaining after the addition reaction, located closer to Rf 4 .
  • the resulting Rf 3 —CF ⁇ CR 3 —CHR 4 —CF 2 —Rf 4 —I can be further subjected to HF-elimination to provide Rf 3 —CF ⁇ CR 3 —CR 4 ⁇ CF—Rf 4 —I, thereafter Rf 3 —CF ⁇ CR 3 —CR 4 ⁇ CF—Rf 4 —I can be further subjected to addition with ethylene, the resulting Rf 3 —CF ⁇ CR 3 —CR 4 ⁇ CF—Rf 4 —CH 2 CH 2 I can be hydrolyzed to synthesize Rf 3 —CR 3 ⁇ CR 4 —Rf 4 —CH 2 CH 2 OH, and thereafter Rf 3 —CR 3 ⁇ CR 4 —Rf 4 —CH 2 CH 2 OH can be bound to a proper introduction material
  • R 3 and R 4 each independently represent a hydrogen atom or a fluorine atom and n represents an integer of 1 to 5. Further preferably, R 3 and/or R 4 represent(s) a hydrogen atom.
  • Z in the general formula (5) represents a surface modification group represented by the following general formula (6) or the following general formula (7).
  • M 3 and M 4 each independently represent a hydrogen atom, an ammonium salt, an organic amine salt, or an alkyl group having 1 to 4 carbon atoms.
  • Such a functional group having an olefin structure sandwiched between perfluoroalkyl chains can be bound to a surface modification group Z via a linking group Y also serving as a spacer portion, thereby synthesizing a compound of interest.
  • the linking group Y is represented by the following general formula (8). (CH 2 ) 1 —Q—(CH 2 ) m (8)
  • the sum of l and m is an integer of 2 to 6; and when l and/or m represents 2 or more, a —CH ⁇ CH— structure is optionally included instead of —CH 2 CH 2 —.
  • Q is absent in the general formula (8), or represents —OCONH—, —CONH—, —O—, —NH—, —CO—O—, —O—CO—, —NHCONH— or —C 6 H 4 —.
  • Q here represents —C 6 H 4 —
  • examples can include an ortho-isomer, a meta-isomer and a para-isomer, and a para-isomer is preferable in terms of the structure thereof.
  • Q is present in the linking group Y, thereby exerting the effect of allowing an intermolecular hydrogen bond and/or ⁇ - ⁇ interaction of Q to act to easily form a unimolecular arrangement of molecules.
  • Q is preferably absent in order to enhance dispersion of a fluorine-containing group in a polymer, and therefore proper Q is needed to be selected depending on the intended use.
  • formation can be easily made according to a conventionally known technique.
  • formation can be made by a reaction of a compound having an isocyanate group at 0.9 to 1.1 times relative to a fluorine-containing alcohol derivative in no solvent or an organic solvent such as dichloromethane or tetrahydrofuran at 1 to 10 times by weight by use of 0.1 to 5 mol % of di-n-butyltin dilaurate or the like as a catalyst at 0° C. to 50° C.
  • the surface modification group Z is a free phosphonyl group (—P( ⁇ O)(OH) 2 ) or a phosphoric acid group (—OP( ⁇ O)(OH) 2 ), or an ester or salt thereof
  • the surface of a metal can be modified and use as a release material of a mold or the like can be made.
  • Z can also represent a polymerizable group.
  • Z represents a polymerizable group
  • the surface of a resin, a film and the like can be modified.
  • the polymerizable group is also not particularly limited in terms of the type thereof, and may be, for example, a vinyl group, an allyl group, a styryl group, a methacryloyl group or an acryloyl group.
  • Z can also represent SiL k L′ (3-k) .
  • L represents a hydrolyzable group or a hydroxyl group
  • L′ represents a hydrocarbon group having 1 to 6 carbon atoms
  • k represents an integer of 1 to 3.
  • the L and L′ groups may be different from or the same as each other.
  • examples include Cl and OR 5 wherein R 5 represents an alkyl group having 1 to 6 carbon atoms.
  • a hydrosilane compound having Si—H can also be used as a bonding group.
  • L′ represents a hydrocarbon group having 1 to 6 carbon atoms, and examples include methyl, ethyl, propyl, vinyl and allyl groups.
  • the L and L′ groups may be different from or the same as each other.
  • the compound described in the present invention can be used to thereby impart water-repellent and oil-repellent properties to the surface of a material, and can be used as a surface modifier.
  • the post-treatment after production of the fluorine-containing compound represented by each of the general formulas (1), (2) and (5) of the present invention can be performed according to a well-known method, and the fluorine-containing compound as a product of interest represented by each of the general formulas (1), (2) and (5) as well as the surface modifier using the compound can be obtained by, for example, obtaining the product of interest by distillation or the like, or obtaining a crude product by a known method such as neutralization, solvent extraction, drying, filtration, condensation or the like, and purifying the crude product by recrystallization, column chromatography or the like.
  • fluorine-containing compound represented by each of the general formulas (1), (2) and (5) of the invention can be used in a modifier as it is, the fluorine-containing compound can also be used with being mixed with other material.
  • fluorine-containing compound can be used with being dissolved in an organic solvent.
  • Modification of the surface of a resin or film in the present invention can be achieved by polymerizing a compound (monomer A) having a polymerizable group described in the present invention and a monomer B having at least one polymerizable group in the molecule in the presence of a polymerization initiator C to provide a fluorine-containing polymer.
  • Examples of the monomer B include the following compounds (X 1 ) to (X 9 ):
  • acetic acid propionic acid, caprylic acid, lauric acid, stearic acid, behenic acid and the like;
  • styrene-based compounds styrene, ⁇ -methylstyrene, p-methylstyrene and the like;
  • the monomer B is preferably a (meth)acrylic acid ester, in particular, a (meth)acrylic acid alkyl ester.
  • the number of carbon atoms in such an alkyl group is preferably 1 to 30, more preferably 1 to 20.
  • the monomer B not only a non-fluorine monomer, for example, a (meth)acrylic acid ester, but also a halogen monomer (in particular, a chlorine- or fluorine-containing monomer, for example, vinyl chloride, vinylidene fluoride or tetrafluoroethylene) may be used.
  • a non-fluorine monomer for example, a (meth)acrylic acid ester
  • a halogen monomer in particular, a chlorine- or fluorine-containing monomer, for example, vinyl chloride, vinylidene fluoride or tetrafluoroethylene
  • the amount of the monomer B to be used is preferably 1 to 1000 parts by weight, more preferably 10 to 100 parts by weight per 100 parts by weight of the monomer A.
  • an azo-based polymerization initiator is preferably used as the polymerization initiator C.
  • the azo-based polymerization initiator include the following compounds (Y 1 ) to (Y 6 ):
  • 2,2′-azobisisobutyronitrile 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2-(carbamoylazo)isobutyronitrile and the like;
  • an initiator having a substituent relatively low in polarity is desirable from the viewpoint of the surface energy of a fluorine-containing highly branched polymer to be obtained, and in particular, 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate or 2,2′-azobis(2,4,4-trimethylpentane) is preferable.
  • the polymerization initiator C is used in an amount of 0.1 to 200 mol % based on the total molar number of the monomer A and the monomer B, and is preferably used in an amount of 0.5 to 100 mol %, more preferably 0.5 to 50 mol %, most preferably 0.5 to 20 mol %.
  • organic solvent examples include aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethyl benzene and tetralin; aliphatic or alicyclic hydrocarbon-based solvents such as n-hexane, n-heptane, mineral spirit and cyclohexane; halogen-based solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene and o-dichlorobenzene; ester-based or ester ether-based solvents such as ethyl acetate, butyl acetate, methoxy butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate and propylene glycol monomethyl ether acetate; ether-based solvents such as diethyl
  • the content of the organic solvent in the entire polymerization reaction product is preferably 1 to 100 parts by mass, further preferably 5 to 50 parts by mass per part by mass of the monomer A.
  • the polymerization reaction is performed at ordinary pressure, under a pressurized and sealed condition, or under reduced pressure, and is preferably performed at ordinary pressure from the viewpoint of simplicity of an apparatus and an operation.
  • the reaction is preferably performed under an atmosphere of an inert gas such as N 2 .
  • the temperature of the polymerization reaction is preferably 50 to 200° C., further preferably 70 to 150° C.
  • the resulting fluorine-containing polymer is recovered according to any method and, if necessary, subjected to a post-treatment such as washing.
  • a post-treatment such as washing.
  • the method for recovering a polymer from a reaction solution include a method such as reprecipitation.
  • the weight average molecular weight (hereinafter, abbreviated as Mw) of the resulting fluorine-containing polymer is preferably 1,000 to 200,000, further preferably 2,000 to 100,000, most preferably 5,000 to 60,000 in terms of polystyrene by gel permeation chromatography (GPC).
  • Preparation of a release agent by use of the phosphonyl group- or phosphoric acid (ester) group-containing compound obtained in the present invention is performed by dilution with water or an organic solvent so as to provide an aqueous solution, an aqueous dispersion liquid or an organic solvent solution having a concentration of about 0.01 to 30% by weight, preferably about 0.05 to 3% by weight.
  • the organic solvent used is at least one of alcohols such as methanol, ethanol, n-propanol and isopropanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, polyols or ethers thereof, such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether and glycerin, polyhydric alcohol derivatives such as methyl cellosolve, ethyl cellosolve, methyl carbitol
  • the organic solvent can also be here used in combination with water.
  • release agent can also be, if necessary, added an amine-based neutralizing agent such as triethylamine, triethanolamine, tris(2-hydroxyethyl)amine and morpholine, various surfactants for improving wettability of the release agent, such as an ionic surfactant and a nonionic surfactant, silicone oil and silicone varnish for further improving releasability and lubricity, and the like.
  • the amine-based neutralizing agent is used in a proportion of about 0.01 to 300% by weight in the total amount of the amine-based neutralizing agent, a phosphonyl group- or phosphoric acid group-containing compound, and water, an organic solvent, or both of them.
  • the mold can be coated with the release agent solution by any method commonly used, such as coating by dipping, spraying, brush coating, aerosol propelling or an impregnated cloth.
  • the molding material formed in the mold coated with the release agent include resins such as polyurethane, polycarbonate, an epoxy resin, a phenol resin, a polyimide resin and a vinyl chloride resin, and rubbers such as natural rubber, chloroprene rubber and fluororubber.
  • the present invention can provide a fluorine-containing compound having a different structure from that of a conventional modification material compound and exerting extremely high water-repellent and oil-repellent effects, as well as a surface modifier using the compound.
  • GC-MS GCMS-QP2010Plus (Shimadzu Corporation)
  • a 100-ml eggplant flask was charged with 150 g (294 mol) of 3,3,4,4,5,5,6,6-octafluoro-1,8-diiodooctane ( ⁇ 1 ) (reagent of SynQuest Laboratories) and 150 g of THF, and dissolved. After cooling to 5° C. or less, a liquid in which 44.8 g (294 mmol) of diazabicycloundecene was dissolved in 25 g of THF was placed over 1 hour with stirring.
  • the resulting light yellow slurry was heated and dissolved in hexane and thereafter crystallized by cooling, a crystal precipitated was removed, and the solvent of a filtrate was removed under reduced pressure and thereafter distillated under reduced pressure, to provide 52.9 g of light pink oily compound (1).
  • a 150-ml SUS autoclave was charged with 61.3 g (137.4 mmol) of 1-iodoperfluorohexane ( ⁇ 2 ) (reagent of Tokyo Chemical Industry Co., Ltd.), 50.0 g (130.9 mmol) of 3,3,4,4,5,5,6,6-octafluoro-8-iodo-1-octene (1) and 0.19 g (1.3 mmol) of di-tert-butyl peroxide, the autoclave was sufficiently purged with nitrogen, and thereafter the temperature was raised to conduct the reaction at 120° C. for 2 hours with stirring.
  • reaction liquid was subjected to distillation under reduced pressure, to provide 26.7 g of compound (2) being a colorless and transparent liquid as a fraction at 85 to 90° C. (2 kPa).
  • the reaction was conducted at room temperature with stirring overnight, and thereafter 100 g of a 1% by weight hydrochloric acid solution was added to separate an aqueous phase.
  • An organic phase was washed with water, 1% by weight potassium hydrogen carbonate, and saturated saline, thereafter the solvent was removed, and the resultant was treated with silica and then subjected to distillation under reduced pressure, to obtain 19.0 g of compound (3) being a colorless and transparent liquid as a fraction at 90 to 94° C. (2 kPa).
  • the yield was 90.1%.
  • a 150-ml SUS autoclave was charged with 88.42 g (0.36 mol) of 3,3,4,4,5,5,6,6,6-nonafluoro-1-octene ( ⁇ 3 ) (reagent of Tokyo Chemical Industry Co., Ltd.), 199.00 g (0.36 mol) of 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane ( ⁇ 4 ) (produced by Tosoh F-Tech, Inc.) and 0.53 g (0.004 mol) of di-tert-butyl peroxide, and the autoclave was purged with nitrogen.
  • a 100-ml eggplant flask was charged with 10.00 g (14.45 mmol) of compound (5) and 7.7 g of an aqueous 25% by weight sodium disulfite solution, and the flask was sufficiently purged with nitrogen.
  • the inner temperature was raised to 70° C., and a solution in which 0.05 g (0.30 mmol) of azobisisobutyronitrile was dissolved in 1.01 g (17.34 mmol) of allyl alcohol ( ⁇ 5 ) was slowly dropped under vigorous stirring over 1 hour with the inner temperature being kept at 75 to 85° C. After the dropping, the reaction was performed at 75° C. for 16 hours, and thereafter the resultant was treated at 100° C. for 10 minutes.
  • a 150-ml SUS autoclave was charged with 31.24 g (0.090 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-nonafluoro-1-decene ( ⁇ 6 ) (reagent of Tokyo Chemical Industry Co., Ltd.), and 50.00 g (0.090 mol) of 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane ( ⁇ 4 ) (produced by Tosoh F-Tech, Inc.) and 0.13 g (0.001 mol) of di-tert-butyl peroxide, and the autoclave was purged with nitrogen.
  • a 100-ml two-necked flask was charged with 65.21 g of a mixture including (8) obtained in the reaction, and 55.71 g of a 10% potassium hydroxide-methanol solution was dropped under room temperature over 15 minutes. After the reaction at room temperature for 1 hour, the reaction liquid was washed with 50 g of water, 50 g of an aqueous 10% ammonium chloride solution and 50 g of saturated saline. The organic layer was diluted with dichloromethane. Furthermore, the organic layer was washed with g of 1% hydrochloric acid, 40 g of water and 40 g of saturated saline. The resulting organic layer was subjected to distillation under reduced pressure, to obtain 21.69 g of compound (9) as a fraction at 108° C. and 0.8 kPa. The yield was 31.1%.
  • a 100-ml eggplant flask was charged with 10.00 g (12.95 mmol) of compound (9) and 6.9 g of an aqueous 25% by weight sodium disulfite solution, and the flask was sufficiently purged with nitrogen.
  • the inner temperature was raised to 70° C., and a solution in which 0.04 g (0.27 mmol) of azobisisobutyronitrile was dissolved in 0.90 g (15.54 mmol) of allyl alcohol ( ⁇ 5 ) was slowly dropped under vigorous stirring over 1 hour with the inner temperature being kept at 75 to 85° C. After the dropping, the reaction was performed with stirring at 75° C. for 16 hours, and thereafter the resultant was treated at 100° C. for 10 minutes.
  • a 150-ml SUS autoclave was charged with 76 g (0.22 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octene ( ⁇ 6 ) (reagent of Tokyo Chemical Industry Co., Ltd.), and 200 g (0.44 mol) of 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane ( ⁇ 7 ) (produced by Tosoh F-Tech, Inc.) and 0.65 g (0.004 mol) of di-tert-butyl peroxide, and the autoclave was purged with nitrogen.
  • a 100-ml eggplant flask was charged with 27.75 g (34.7 mmol) of compound (12) and 18.5 g of an aqueous 25% by weight sodium disulfite solution, and the flask was sufficiently purged with nitrogen.
  • the inner temperature was raised to 70° C., and a solution in which 0.12 g (0.73 mmol) of azobisisobutyronitrile was dissolved in 4.03 g (69.4 mmol) of allyl alcohol ( ⁇ 5 ) was slowly dropped under vigorous stirring over 2 hours with the inner temperature being kept at 75 to 85° C. After the dropping, the reaction was performed with stirring at 75° C. for 16 hours, and thereafter the resultant was treated at 100° C. for 10 minutes.
  • the crude product included 19.3% of raw material (12), 17.2% of reduced product (14) with one iodine and 10.6% of 2-adduct (15). Each calculation was made depending on the area percentage by GC.
  • the resulting orange oily product was purified and separated by a silica column chromatographic method (filler: silica gel 60N produced by Kanto Kagaku, eluent: dichloromethane) to obtain 0.32 g of compound (20).
  • the yield from compound (12) was 1.5%.
  • a 500-ml three-necked flask was charged with 6.09 g (225.90 mol) of an aluminum powder (reagent of Wako Pure Chemical Industries, Ltd.), 5.37 g (22.59 mmol) of nickel chloride hexahydrate (reagent of Wako Pure Chemical Industries, Ltd.), 177 g of acetonitrile and 40.00 g (113.0 mmol) of 3,3,4,4,5,5,6,6,7,7,8,8-dodecafluorooctadecyl-1,9-diene ( ⁇ 8 ) (produced by Tosoh F-Tech, Inc.), and 50.37 g (446.0 mol) of 1-iodo-1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane ( ⁇ 2 ) was dropped under room temperature over 15 minutes.
  • a 10-ml vial was charged with 5.00 g of compound (17), and 4.67 g of a 10% potassium hydroxide-methanol solution was dropped under room temperature over 5 minutes. After the reaction at room temperature for 1 hour, the reaction liquid was washed with 5 g of an aqueous 10% ammonium chloride solution, 5 g of water and 5 g of saturated saline. The resulting organic layer was condensed under reduced pressure to obtain 4.46 g of compound (19). The yield was 93.9%.
  • the resulting compound (20) was analyzed, and the following results were obtained.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 1.00 g (1.7 mmol) of compound (3), 0.004 g (0.01 mmol) of chloroplatinic acid hexahydrate (reagent of Wako Pure Chemical Industries, Ltd.) and 0.45 g (3.3 mmol) of trichlorosilane (reagent of Tokyo Chemical Industry Co., Ltd.), and the reaction was performed under stirring at 50° C. for 3 days.
  • the reaction was conducted with stirring at room temperature for 2 hours, and purification was performed by a silica column chromatographic method (filler: silica gel 60N produced by Kanto Kagaku, eluent: hexane) to provide 0.33 g of the product of interest (24). The yield was 93.3%.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 1.00 g (1.53 mmol) of compound (17), 0.008 g (0.02 mmol) of chloroplatinic acid hexahydrate (reagent of Wako Pure Chemical Industries, Ltd.) and 0.31 g (2.29 mmol) of trichlorosilane (reagent of Tokyo Chemical Industry Co., Ltd.), and the reaction was performed under stirring at 50° C. for 15 hours.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 2.00 g (3.06 mmol) of compound (17), 0.012 g (0.03 mmol) of a Karstedt catalyst (reagent of Tokyo Chemical Industry Co., Ltd.) and 0.60 g (3.67 mmol) of triethoxysilane (reagent of Tokyo Chemical Industry Co., Ltd.), and the reaction was performed under stirring at 80° C. for 15 hours.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 1.00 g (1.63 mmol) of compound (19), 0.008 g (0.02 mmol) of chloroplatinic acid hexahydrate (reagent of Wako Pure Chemical Industries, Ltd.) and 0.33 g (2.44 mmol) of trichlorosilane (reagent of Tokyo Chemical Industry Co., Ltd.), and the reaction was performed under stirring at 50° C. for 15 hours.
  • the reaction was conducted under a nitrogen atmosphere with stirring at room temperature for 65 hours, purification was performed by a silica column chromatographic method (filler: silica gel 60N produced by Kanto Kagaku, eluent: hexane-ethyl acetate 95/5 (volume/volume)) to provide 0.75 g of the compound of interest (28).
  • the yield was 55.3%.
  • the resulting compound (28) was analyzed, and the following results were obtained.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 1.00 g (1.42 mmol) of compound (11), 4.7 g of dichloromethane and 0.22 g (2.13 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.28 g (2.13 mmol) of methacryloyl chloride ( ⁇ 12 ) (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 0.50 g (0.71 mmol) of compound (11), 2.4 g of dichloromethane and 0.11 g (1.07 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.12 g (1.07 mmol) of acryloyl chloride ( ⁇ 13 ) (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 0.50 g (0.74 mmol) of compound (18), 2.5 g of dichloromethane and 0.11 g (1.12 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.15 g (1.12 mmol) of methacryloyl chloride ( ⁇ 12 ) (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 0.44 g (0.67 mmol) of compound (20), 2.2 g of dichloromethane and 0.10 g (1.01 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.13 g (1.01 mmol) of methacryloyl chloride ( ⁇ 12 ) (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 1.00 g (1.42 mmol) of compound (11), 4.7 g of dichloromethane and 0.43 g (4.26 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.74 g (4.26 mmol) of diethyl chlorophosphate (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 0.50 g (0.74 mmol) of compound (18), 2.5 g of dichloromethane and 0.23 g (2.23 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.39 g (2.23 mmol) of diethyl chlorophosphate (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes. After the reaction was performed under stirring at room temperature for 1 hour, the solvent was removed by nitrogen bubbling, and the reaction liquid was diluted with 20 g of diisopropyl ether and washed with 20 g of saturated saline three times.
  • a glass pressure-resistant tube (manufactured by Ace Glass Inc.: 40 ml) was charged with 0.25 g (0.39 mmol) of compound (20), 1.3 g of dichloromethane and 0.12 g (1.18 mmol) of triethylamine (reagent of Wako Pure Chemical Industries, Ltd.), and 0.39 g (2.23 mmol) of diethyl chlorophosphate (reagent of Tokyo Chemical Industry Co., Ltd.) was dropped under stirring at 0° C. over 5 minutes. After the reaction was performed under stirring at room temperature for 1 hour, the solvent was removed by nitrogen bubbling, and the reaction liquid was diluted with 20 g of diisopropyl ether and washed with 20 g of saturated saline three times.
  • the yield was 86.5%.
  • a glass slide (manufactured by Matsunami Glass Ind., Ltd., size: 76 mm ⁇ 26 mm ⁇ 1.2 mm) was immersed in a saturated potassium hydroxide-isopropyl alcohol solution at room temperature for 17 hours, washed with water and dried at 60° C. for 2 hours before use, and the resultant was immediately used as a pre-treated glass.
  • This pre-treated glass was treated with being stirred and immersed in a surface modifier solution, in which compound (21) synthesized in Example 8 was dissolved in a chloroform solvent so as to be in an amount of 0.3% by weight, at 50° C. for 2 hours.
  • the glass was taken out from the modification solution, an excessive surface modifier attached to the glass surface was wiped off by Novec (registered trademark) 7100 (produced by 3M) and water, and thereafter the resultant was treated at 150° C. for 2 hours to provide a surface-modified glass substrate.
  • the contact angle was determined by dropping 1 ⁇ L of a droplet onto the surface of the surface-modified glass substrate, imaging the resultant as viewed edge-on, and subjecting the resulting projected image to a ⁇ /2 method.
  • the contact angle was measured by using compound (22) synthesized in Example 9 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
  • the contact angle was measured by using compound (23) synthesized in Example 10 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
  • the contact angle was measured by using compound (24) synthesized in Example 11 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
  • the contact angle was measured by using compound (25) synthesized in Example 12 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
  • the contact angle was measured by using compound (26) synthesized in Example 13 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
  • the contact angle was measured by using compound (27) synthesized in Example 14 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
  • the contact angle was measured by using compound (28) synthesized in Example 15 instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
  • the contact angle was measured by using CF 3 (CF 2 ) 5 CH 2 CH 2 Si (OMe) 3 (produced by Sigma-Aldrich) as a comparative agent instead of compound (21) to modify the surface of the glass slide in the same manner as in Example 24.
  • the remaining precipitate was again dissolved in 3.5 g of tetrahydrofuran, and the solution was added to 42.4 g of hexane to reprecipitate a polymer.
  • the precipitate was subjected to suction filtration, and dried in vacuum to provide 0.92 g of the product of interest (polymer 1) as a white powder.
  • the yield was 60.5%.
  • the weight average molecular weight Mw and the dispersibility Mw/Mn of the resulting product of interest, in terms of polystyrene measured by GPC, were 17,000 and 1.5, respectively.
  • the remaining precipitate was again dissolved in 3.5 g of tetrahydrofuran, and the solution was added to 42.4 g of hexane to reprecipitate a polymer.
  • the precipitate was subjected to suction filtration, and dried in vacuum to provide 0.95 g of the product of interest (polymer 2) as a white powder.
  • the yield was 61.7%.
  • the weight average molecular weight Mw and the dispersibility Mw/Mn of the resulting product of interest, in terms of polystyrene measured by GPC, were 32,000 and 2.0, respectively.
  • the remaining precipitate was again dissolved in 3.5 g of tetrahydrofuran, and the solution was added to 42.4 g of hexane to reprecipitate a polymer.
  • the precipitate was subjected to suction filtration, and dried in vacuum to provide 0.85 g of the product of interest (polymer 3) as a white powder.
  • the yield was 55.2%.
  • the weight average molecular weight Mw and the dispersibility Mw/Mn of the resulting product of interest, in terms of polystyrene measured by GPC, were 18,000 and 1.7, respectively.
  • the remaining precipitate was again dissolved in 3.5 g of tetrahydrofuran, and the solution was added to 42.4 g of hexane to reprecipitate a polymer.
  • the precipitate was subjected to suction filtration, and dried in vacuum to provide 0.81 g of the product of interest (polymer 4) as a white powder.
  • the yield was 52.6%.
  • the weight average molecular weight Mw and the dispersibility Mw/Mn of the resulting product of interest, in terms of polystyrene measured by GPC, were 19,000 and 1.6, respectively.
  • the reaction liquid was dropped to 151.5 g of hexane to precipitate a polymer, and the supernatant solution was subjected to decantation. The remaining precipitate was again dissolved in 12.5 g of tetrahydrofuran, and the solution was added to 151.5 g of hexane to reprecipitate a polymer. The precipitate was subjected to suction filtration, and dried in vacuum to provide 2.01 g of the product of interest (polymer 5) as a white powder. The yield was 52.2%.
  • the weight average molecular weight Mw and the dispersibility Mw/Mn of the resulting product of interest, in terms of polystyrene measured by GPC, were 21,000 and 2.0, respectively.
  • a thin film was formed in the same manner as in Example 36 by use of polymer 2 synthesized in Example 33 instead of polymer 1, and the contact angle thereof was measured.
  • a thin film was formed in the same manner as in Example 36 by use of polymer 3 synthesized in Example 34 instead of polymer 1, and the contact angle thereof was measured.
  • a thin film was formed in the same manner as in Example 36 by use of polymer 4 synthesized in Example 35 instead of polymer 1, and the contact angle thereof was measured.
  • a thin film was formed in the same manner as in Example 36 by use of polymer 5 synthesized in Comparative Example 3 instead of polymer 1, and the contact angle thereof was measured.
  • An aqueous release agent solution including 0.5% by weight of compound (33) obtained in Example 20, 49.8% by weight of pure water and 49.7% by weight of isopropanol was prepared.
  • the release agent solution was used to perform evaluation of releasability according to the following measurement method.
  • a polyurethane prepolymer and a curing agent were poured into a mold (made of aluminum, 60 mm in diameter and 50 mm in depth) coated with the release agent, and cured under a heated and pressurized condition, and thereafter the load at which a molded product was released from the mold was measured by a push-pull scale.
  • the releasability in a case where the load required was less than 10 N was rated as “Excellent”, that in a case where the load was 10 N or more and less than 20 N was rated as “Good”, that in a case where the load was 20 N or more and less than 50 N rated as “Fair”, and that in a case where the load was 50 N or more was rated as “Poor”.
  • the number of times where releasing was possible under a load of less than 50 N under the same condition was measured and defined as the repeatability.
  • novel fluorine-containing compound and the surface modifier using the compound, of the present invention exhibit high water repellency and oil repellency, and can be utilized in surface modifiers such as a release agent and a antifouling agent.

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US16/025,014 2016-01-08 2018-07-02 Fluorine-containing compound having unsaturated bond, and surface modifier using the same Active 2039-05-25 US11352457B2 (en)

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